US4209554A - Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith - Google Patents
Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith Download PDFInfo
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- US4209554A US4209554A US06/014,131 US1413179A US4209554A US 4209554 A US4209554 A US 4209554A US 1413179 A US1413179 A US 1413179A US 4209554 A US4209554 A US 4209554A
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- 239000011521 glass Substances 0.000 title claims abstract description 15
- 150000003839 salts Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 20
- 230000009849 deactivation Effects 0.000 title description 3
- 239000002184 metal Substances 0.000 title 1
- -1 aralkyl halides Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000003003 phosphines Chemical class 0.000 claims abstract description 8
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- TXFNTLLEAYZBGV-UHFFFAOYSA-N 2-diphenylphosphanylethyl-[2-[2-diphenylphosphanylethyl(phenyl)phosphanyl]ethyl]-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 TXFNTLLEAYZBGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- AXVOAMVQOCBPQT-UHFFFAOYSA-N triphos Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 AXVOAMVQOCBPQT-UHFFFAOYSA-N 0.000 claims description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- TVLNGWSWPKIYAO-UHFFFAOYSA-N tris(2-diphenylphosphanylethyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(CCP(C=1C=CC=CC=1)C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 TVLNGWSWPKIYAO-UHFFFAOYSA-N 0.000 claims description 3
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical group BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 claims description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 5
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 9
- 238000011282 treatment Methods 0.000 abstract description 3
- 238000004817 gas chromatography Methods 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 8
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 6
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- WTEVQBCEXWBHNA-YFHOEESVSA-N citral B Natural products CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 description 5
- 238000005956 quaternization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000005308 flint glass Substances 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000134874 Geraniales Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- MFSBVCLAVKRWMC-UHFFFAOYSA-N arsanylphosphane Chemical class [AsH2]P MFSBVCLAVKRWMC-UHFFFAOYSA-N 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OPEJZUZBJHDLPL-UHFFFAOYSA-M methyl(trioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC OPEJZUZBJHDLPL-UHFFFAOYSA-M 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CLTOYDRANCCRLQ-UHFFFAOYSA-M tetrabenzylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[P+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 CLTOYDRANCCRLQ-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/025—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with wetted adsorbents; Chromatography
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5449—Polyphosphonium compounds
Definitions
- This invention relates to new polydentate salts prepared from polydentate phosphines containing at least two and preferably at least four trivalent phosphorus atoms or their antimony or arsenic analogs and their use in deactivating glass capillary columns for high temperature analysis of polar compounds via gas chromatographic techniques.
- a primary object of this invention is to prepare novel phosphonium salts by the quaternization of polydentate phosphines containing two or more trivalent phosphorus atoms.
- Another object relates to a process for treating glass capillary surfaces with one or more of the herein described phosphonium salts or their antimony or arsenic analogs.
- a further object relates to a process for deactivating capillary columns and the use of such deactivated columns in the gas chromatographic analysis of complex mixtures including polar compounds at operating temperatures of 300° C. and above.
- a further object relates to a process for preparing a glass capillary column capable of resolving complex mixtures of polar compounds at useful temperatures of 300° C. and above:
- the polydentate phosphonium salts of the instant invention can be prepared by usual quaternization techniques.
- the polydentate can be dissolved in a solvent and one equivalent (per each trivalent phosphonium atom) of alkyl halide or aralkyl halide in a solvent added slowly thereto with stirring under a reflux condenser and an inert atmosphere followed by stirring and reflux as needed to complete the reaction.
- excess halide can be used as the reaction medium, in which case the polydentate is added directly thereto.
- the reaction products are usually crystalline solids which may be isolated by filtration and purified by recrystallization.
- Polydentate compounds useful in the practice of this invention include those obtained by partial or complete quaternization of polydentate phosphines containing two or more trivalent phosphorus atoms or their antimony or arsenic analogs.
- the following structures are representative of such polydentate compounds:
- R 1 R 2 MA MAM(AMR 1 R 2 ) 2 ; and ##STR1## wherein M is independently a group V-A element selected from the group consisting of phosphorus, antimony and arsenic; R 1 , R 2 and R 3 are the same or different C 1-20 alkyl radicals or aromatic radicals containing up to twelve carbon atoms; and A represents a lower alkylene radical containing from 2 to 6 carbons, and n is an integer from 1 to 6.
- Useful quaternary salt forming compounds include mono or difunctional alkyl or aralkyl halide selected from the group consisting of (1) R 4 X; (2) ArR 5 X; (3) XR 6 X; and (4) XCH 2 ArCH 2 X wherein X is halogen; R 4 is an alkyl radical containing up to 20 carbon atoms; R 5 is a lower alkylene radical containing 1 to 4 carbon atoms; and R 6 is a lower alkylene radical containing 2 to 6 carbon atoms; Ar is a monovalent or divalent aryl radical which may contain one or more halogen ring substituents and when Ar is a divalent radical, the compound may contain one or more aryl groups.
- phosphonium salts are preferred because of the stability and availability of the polytertiary phosphines.
- Useful polydentates include those exemplified in U.S. Pat. No. 3,130,237 (Wald) and the phosphines, arsines and arsinophosphines described by King and Kapoor in U.S. Pat. No. 3,657,298.
- Flint glass capillary columns were drawn using a Schimadzu GDM-1 capillary drawing machine and then etched with a hydrogen halide at a temperature in the range of 300°-450° C. for 1 to 4 hours. After cooling to ambient temperature, a solution of the phosphonium halide dissolved in a solvent is then percolated through the column under positive nitrogen atmosphere. Nitrogen flow is continued and the column allowed to dry. The column is then treated with the appropriate liquid substrate in a solvent, dried under nitrogen and conditioned by further heating until a stable base line is obtained. The above treatment will result in uniformly treated columns which may be operated routinely at 300° C. and above, at high column efficiency with no substantial peak tailing.
- the alkyl and aralkyl halides useful in preparing the phosphonium salts of this invention include the fluorides, chlorides, bromides and iodides of C 1-20 alkyl halides and aralkyl halides.
- the aryl moiety may have one or more substituents in the aromatic ring portion selected from the group consisting of lower alkyl and halogen, provided they do not interfere with the quaternization reaction.
- Preferred mono functional halides include methyl, ethyl, and benzylbromides, chlorides, fluorides and iodides with the bromides being especially advantageous because of their availability and reactivity.
- halides are double ended halides of the formula X--R--X.
- Preferred multifunctional halides include 1,2-dibromoethane; 1,3-dibromopropane; 1,4-dibromobutane; and ⁇ , ⁇ '-dibromo-p-xylene with the latter two compounds being especially preferred.
- Phosphonium compounds selected from multifunctional halides will generally be highly cross-linked and thus having a higher decomposition temperature. They are generally soluble in polar solvents from which they may be purified by recrystallization techniques.
- a flint glass capillary column approximately 60 meters in length and 0.25 mm in internal diameter was fabricated using a Shimadzu GDM-1 glass drawing machine.
- the column was etched with hydrogen chloride gas at 350° C. for 2 hours according to the method described by Franken et al., J. Chromatog; 126, 117-132 (1976).
- 3 ml of a 1 percent solution of the phosphonium salt of Example 1 dissolved in dimethylsulfoxide was passed through the column immediately followed by 2 ml of a 15 percent solution of SP-2100 (Supelco Inc.) dissolved in methylene chloride using the mercury plug technique as described by G. Schombey et al, Chromatographia 8, 486 (1975).
- a second column using SP-2100 substrate but deactivated with benzyltriphenylphosphonium chloride was prepared under identical conditions.
- the column deactivated with the salt 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane was usable at operating temperatures programmable to 300° C. and above whereas the column deactivated with benzyltriphenylphosphonium chloride rapidly deteriorated at this temperature.
- Two 20 m glass capillary columns were prepared according to the procedure of Example 5 using 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane and benzyltriphenylphosphonium chloride deactivators respectively. Each column was evaluated using a Hewlett-Packard Model No. 5750 gas chromatograph having a flame ionization detector. The columns were conditioned at 275° C. for 16 hours under a helium gas flow.
- the column deactivated with the compound of Example 1 exhibited greatly improved peak symmetry (reduced tailing) over the column deactivated with benzyltribenzylphosphonium chloride.
- Example 6 The comparative experiment as described in Example 6 was repeated using a more complex mixture containing the cis trans isomers Citral A (neral) and Citral B (geranial).
- the column deactivated with the compound of Example 1 gave markedly improved resolution and substantially no peak tailing as contrasted to the column deactivated with benzyltriphenylphosphonium chloride.
- the respective graphs of peak heights v. time are shown in FIG. 1. The major peaks represent Citral A (left) and Citral B (right).
- the temperature dependence of various deactivation treatments was determined by connecting a treated but uncoated (no substrate) column and raising the temperature to the desired test temperature. After heating for a period of 3 hours, the temperature was lowered to 150° C. and a series of six compounds-each representing a different chemical functionality-was evaluated. The degree of deactivation was expressed as the tailing factor as described by Schiehe and Pretorius, J. Chromatog; 132, 217 (1977).
- the test compounds were (a) n-decane; (b) n-hexanol; (c) 2-nonanone; (d) 2,5-dimethylaniline; (d) salicylaldehyde; and (f) linalyl acetate.
- the average tailing factor for each of the deactivator compounds are given below:
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Abstract
Phosphonium salts are prepared by reacting polydentate phosphines containing two or more trivalent phosphorus atoms with alkyl or aralkyl halides. Treatment of glass surfaces and glass capillary columns with these salts substantially eliminates tailing of peaks and allow the high temperature separation and characterization of polar compounds by gas chromatography at temperatures of 300° C.
Description
This invention relates to new polydentate salts prepared from polydentate phosphines containing at least two and preferably at least four trivalent phosphorus atoms or their antimony or arsenic analogs and their use in deactivating glass capillary columns for high temperature analysis of polar compounds via gas chromatographic techniques.
Gas chromatography techniques using glass capillary columns in conjunction with flame ionization detectors have developed as an analytical tool over the past two decades. Complex mixtures of hydrocarbons can be separated into their component parts using open tubular columns. The use of glass as a base material for capillary columns is advantageous because of its low catalytic activity and relative inertness to labile substances in complex mixtures. Such columns suffer from the disadvantage that components of polar mixtures are more strongly attached to the column wall. Thus, when the operating temperature is increased above 150° C. the carrier gas tends to dislodge the column liquid phase from the glass surface causing decreased resolution by peak tailing.
This problem has been partly resolved by adding surface active material to the liquid coating phase to eliminate the effect of column wall. Various surfactants thus increased the useful operating temperature to about 170° C. Other techniques (Metcalf, L.D. and Martin, R. J., Anal. Chem. 1204 [1967]) using trioctadecylmethylammonium bromide as an additive extended the useful temperature range of capillary columns to about 200° C. By combining benzyltriphenylphosphonium chloride with various high temperature phases, Malec [J. Chromatog. Sci., 9, 319 (1971)] was successful in overcoming resolution difficulties and produced columns useful at about 250° C. In the gas chromatographic analysis of polar mixtures, there is a need to provide capillary columns that will withstand even higher temperatures whereby substrate bleeding and peak tailing is eliminated using columns operated routinely at 300° C. and above.
A primary object of this invention is to prepare novel phosphonium salts by the quaternization of polydentate phosphines containing two or more trivalent phosphorus atoms.
Another object relates to a process for treating glass capillary surfaces with one or more of the herein described phosphonium salts or their antimony or arsenic analogs.
A further object relates to a process for deactivating capillary columns and the use of such deactivated columns in the gas chromatographic analysis of complex mixtures including polar compounds at operating temperatures of 300° C. and above.
A further object relates to a process for preparing a glass capillary column capable of resolving complex mixtures of polar compounds at useful temperatures of 300° C. and above:
(a) by etching the glass surface with a hydrogen halide;
(b) contacting the etched surface with a solution of one or more polydentate phosphonium salts containing two or more and preferably at least four trivalent phosphorus atoms to deactivate the glass surface;
(c) treating the deactivated columns with one or more liquid phases capable of resolving said complex polar compounds;
(d) thereafter drying the column and conditioning the dried column at a temperature of about 300° C. and above.
Other and further objects, features and advantages of this invention will appear more fully from the following description.
The polydentate phosphonium salts of the instant invention can be prepared by usual quaternization techniques. The polydentate can be dissolved in a solvent and one equivalent (per each trivalent phosphonium atom) of alkyl halide or aralkyl halide in a solvent added slowly thereto with stirring under a reflux condenser and an inert atmosphere followed by stirring and reflux as needed to complete the reaction. Alternatively, excess halide can be used as the reaction medium, in which case the polydentate is added directly thereto. The reaction products are usually crystalline solids which may be isolated by filtration and purified by recrystallization.
Polydentate compounds useful in the practice of this invention include those obtained by partial or complete quaternization of polydentate phosphines containing two or more trivalent phosphorus atoms or their antimony or arsenic analogs. The following structures are representative of such polydentate compounds:
(1) R1 R2 MAMR1 R2 ;
(2) (R1 R2 MA)3 P;
(3) (R1 R2 MA)2 MR3 ;
(4) (R1 R2 MA)2 MAM(AMR1 R2)2 ; and ##STR1## wherein M is independently a group V-A element selected from the group consisting of phosphorus, antimony and arsenic; R1, R2 and R3 are the same or different C1-20 alkyl radicals or aromatic radicals containing up to twelve carbon atoms; and A represents a lower alkylene radical containing from 2 to 6 carbons, and n is an integer from 1 to 6. Useful quaternary salt forming compounds include mono or difunctional alkyl or aralkyl halide selected from the group consisting of (1) R4 X; (2) ArR5 X; (3) XR6 X; and (4) XCH2 ArCH2 X wherein X is halogen; R4 is an alkyl radical containing up to 20 carbon atoms; R5 is a lower alkylene radical containing 1 to 4 carbon atoms; and R6 is a lower alkylene radical containing 2 to 6 carbon atoms; Ar is a monovalent or divalent aryl radical which may contain one or more halogen ring substituents and when Ar is a divalent radical, the compound may contain one or more aryl groups.
In the instant invention, phosphonium salts are preferred because of the stability and availability of the polytertiary phosphines. Useful polydentates include those exemplified in U.S. Pat. No. 3,130,237 (Wald) and the phosphines, arsines and arsinophosphines described by King and Kapoor in U.S. Pat. No. 3,657,298.
Flint glass capillary columns were drawn using a Schimadzu GDM-1 capillary drawing machine and then etched with a hydrogen halide at a temperature in the range of 300°-450° C. for 1 to 4 hours. After cooling to ambient temperature, a solution of the phosphonium halide dissolved in a solvent is then percolated through the column under positive nitrogen atmosphere. Nitrogen flow is continued and the column allowed to dry. The column is then treated with the appropriate liquid substrate in a solvent, dried under nitrogen and conditioned by further heating until a stable base line is obtained. The above treatment will result in uniformly treated columns which may be operated routinely at 300° C. and above, at high column efficiency with no substantial peak tailing.
The alkyl and aralkyl halides useful in preparing the phosphonium salts of this invention include the fluorides, chlorides, bromides and iodides of C1-20 alkyl halides and aralkyl halides. The aryl moiety may have one or more substituents in the aromatic ring portion selected from the group consisting of lower alkyl and halogen, provided they do not interfere with the quaternization reaction. Preferred mono functional halides include methyl, ethyl, and benzylbromides, chlorides, fluorides and iodides with the bromides being especially advantageous because of their availability and reactivity.
Also contemplated as reactive halides in the quaternization reaction are double ended halides of the formula X--R--X. Preferred multifunctional halides include 1,2-dibromoethane; 1,3-dibromopropane; 1,4-dibromobutane; and α,α'-dibromo-p-xylene with the latter two compounds being especially preferred. Phosphonium compounds selected from multifunctional halides will generally be highly cross-linked and thus having a higher decomposition temperature. They are generally soluble in polar solvents from which they may be purified by recrystallization techniques.
The following examples are intended to illustrate the invention, but not to limit the scope thereof, parts and percentages being by weight unless otherwise indicated.
An excess of benzylbromide, 36 g., was charged to a 50 ml round bottom flask having a stirring bar and fitted with a reflux condenser. 0.5 grams 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane was added and the mixture refluxed under nitrogen for 2 hours. The product was isolated as a light brown precipitate by filtration under a nitrogen blanket.
Calculated for C70 H70 P4 Br4 : C,62.05; H,5.21; P,9.15; Br,23.59. Found: C,59.58; H,5.58; P,9.24; Br,25.61.
In a procedure similar to that given in Example 1, tris(2diphenylphosphinoethyl)phosphine was reacted with excess benzyl bromide. The product was isolated as a brown solid by filtration under a nitrogen blanket.
Calculated for C70 H70 P4 Br4 : C,62.05; H,5.21; P,9.15; Br,23.59. Found: C,62.53; H,5.07; P,9.04; Br,23.35.
Using a procedure similar to that given in Example 1, 1,1,4,7,7-pentaphenyl-1,4,7-triphosphaheptane was reacted with an excess of benzyl bromide. The product was isolated as a white solid.
Using a procedure similar to that given in Example 1, 1,1,4,4-tetraphenyl 1,4-diphosphabutane was reacted with an excess of benzyl bromide. The product, a known compound, was isolated as a white solid.
A flint glass capillary column approximately 60 meters in length and 0.25 mm in internal diameter was fabricated using a Shimadzu GDM-1 glass drawing machine. The column was etched with hydrogen chloride gas at 350° C. for 2 hours according to the method described by Franken et al., J. Chromatog; 126, 117-132 (1976). After cooling 3 ml of a 1 percent solution of the phosphonium salt of Example 1 dissolved in dimethylsulfoxide was passed through the column immediately followed by 2 ml of a 15 percent solution of SP-2100 (Supelco Inc.) dissolved in methylene chloride using the mercury plug technique as described by G. Schombey et al, Chromatographia 8, 486 (1975).
A second column using SP-2100 substrate but deactivated with benzyltriphenylphosphonium chloride was prepared under identical conditions. The column deactivated with the salt 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane was usable at operating temperatures programmable to 300° C. and above whereas the column deactivated with benzyltriphenylphosphonium chloride rapidly deteriorated at this temperature.
Two 20 m glass capillary columns were prepared according to the procedure of Example 5 using 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane and benzyltriphenylphosphonium chloride deactivators respectively. Each column was evaluated using a Hewlett-Packard Model No. 5750 gas chromatograph having a flame ionization detector. The columns were conditioned at 275° C. for 16 hours under a helium gas flow. After cooling to 150° C., a hexane solution containing 1-hexanol, n-decane, 5-nonanone and 2,5-dimethylaniline was analyzed in each column and the respective tailing factors for each component were compared as shown in the following table. It is noted that high tailing factors indicate good resolution, whereas low tailing factors indicate poor resolution and undesirable peak tailing.
______________________________________ Tailing Factor (Average of 2 Evaluations) Benzyltriphenylphosphonium Compound of Chloride Example 1 ______________________________________ 1-hexanol 12.9 66.2 n-decane 95.6 96.9 5-nonanone 27.5 88.6 2,5-dimethylaniline 67.1 88.3 ______________________________________
As indicated, the column deactivated with the compound of Example 1 exhibited greatly improved peak symmetry (reduced tailing) over the column deactivated with benzyltribenzylphosphonium chloride.
The comparative experiment as described in Example 6 was repeated using a more complex mixture containing the cis trans isomers Citral A (neral) and Citral B (geranial). The column deactivated with the compound of Example 1 gave markedly improved resolution and substantially no peak tailing as contrasted to the column deactivated with benzyltriphenylphosphonium chloride. The respective graphs of peak heights v. time are shown in FIG. 1. The major peaks represent Citral A (left) and Citral B (right).
The temperature dependence of various deactivation treatments was determined by connecting a treated but uncoated (no substrate) column and raising the temperature to the desired test temperature. After heating for a period of 3 hours, the temperature was lowered to 150° C. and a series of six compounds-each representing a different chemical functionality-was evaluated. The degree of deactivation was expressed as the tailing factor as described by Schiehe and Pretorius, J. Chromatog; 132, 217 (1977). The test compounds were (a) n-decane; (b) n-hexanol; (c) 2-nonanone; (d) 2,5-dimethylaniline; (d) salicylaldehyde; and (f) linalyl acetate. The average tailing factor for each of the deactivator compounds are given below:
______________________________________ Average Tailing Factor Deactivator (250 ° C.) (275 ° C.) (300 ° C.) ______________________________________ Benzyltriphenylphosphonium Chloride 68 19 -- Toasted Carbowax 20 M 36 14 -- Example 1 - Phosphonium Salt 64 64 47 Example 2 - Phosphonium Salt 70 66 62 Example 3 - Phosphonium Salt 40 38 -- Example 4 - Phosphonium Salt 32 26 -- ______________________________________
Claims (8)
1. A process for deactivating glass capillary columns which comprises treating the internal surfaces of a capillary column with one or more deactivating polydentate salts either prior to or in conjunction with the application of liquid substrate capable of separating complex mixtures of compounds using gas chromatographic techniques wherein the said columns are operated up to 300° C. and above and wherein the salts comprise the reaction product of
(a) a polydentate compound containing two or more quaternizable group V-A elements of the following formula:
(1) R1 R2 MAMR1 R2 ;
(2) (R1 R2 MA)3 M;
(3) (R1 R2 MA)2 MR3 ;
(4) (R1 R2 MA)2 MAM(AMR1 R2)2 ; and ##STR2## wherein M is independently a group V-A element selected from the group consisting of phosphorus, antimony and arsenic; R1, R2 and R3 are the same or different C1-20 alkyl radical, or an aromatic radical containing up to twelve carbon atoms and A represents a straight chain or branched lower alkylene radical containing from 2 to 6 carbons; n is an integer from 1 to 6; and
(b) a quaternary salt forming mono or difunctional alkyl or aralkyl halide selected from the group consisting of (1) R4 X; (2) ArR5 X; (3) XR6 X; and (4) XCH2 MCH2 X wherein X is halogen; R4 is an alkyl radical containing 2 to 6 carbon atoms; R6 is lower alkylene radical containing 2 to 6 carbon atoms; Ar is a mono or divalent aryl radical which may contain one or more halogen ring substituents.
2. The process of claim 1 wherein the polydentate salt is prepared from a phosphine selected from the group consisting of
(a) 1,1,4,4-tetraphenyl 1,4-diphosphabutane;
(b) tris(2-diphenylphosphinoethyl)phosphine;
(c) 1,1,4,7,7-pentaphenyl-1,4,7-triphosphaheptane;
(d) 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane.
3. The process of claim 1 wherein the said phosphines are substantially completely quaternized with benzylbromide.
4. The process of claim 1 wherein the said phosphine is quaternized with 1,4-dibromobutane.
5. The process of claim 1 wherein the said phosphine is quaternized with α,α'-dibromo-p-xylene.
6. The process of claim 3 wherein the phosphine is 1,1,4,7,7-pentaphenyl-1,4,7-triphosphaheptane.
7. The process of claim 3 wherein the phosphine is 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane.
8. A process for preparing glass capillary columns useful in analyzing complex mixtures of compounds by gas chromatographic techniques at operating temperatures up to 300° C. and above which comprises
(a) pretreating the internal surfaces of a capillary column with one or more hydrogen halides at column temperatures in the range of 300° C. to 450° C. for 1 to 4 hours;
(b) cooling the treated column under a nitrogen purge to room temperature;
(c) under a positive inert gas pressure treating the column with a solution of one or more surface deactivating polydentate salts prepared from polydentate phosphines containing two or more trivalent phosphorus atoms or their antimony or arsenic analogs;
(d) drying the column under an inert atmosphere;
(e) coating the cooled column with a liquid substrate useful in separating complex mixtures of organic compounds; and
(f) conditioning the coated column at temperatures up to the maximum operating temperature of the chromatographic substrate.
Priority Applications (2)
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US06/014,131 US4209554A (en) | 1979-02-22 | 1979-02-22 | Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith |
US06/065,588 US4289809A (en) | 1979-02-22 | 1979-09-10 | Polydentate phosphonium salts useful in treating glass and capillary chromatographic columns |
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US06/014,131 US4209554A (en) | 1979-02-22 | 1979-02-22 | Polydentate metal salts used in the process for the deactivation of glass surfaces and capillary columns therewith |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4473505A (en) * | 1980-02-12 | 1984-09-25 | Exxon Research And Engineering Co. | Phosphine and phosphonium compounds and catalysts |
US4620020A (en) * | 1984-04-21 | 1986-10-28 | Hoecht Aktiengesellschaft | Bis-phosphonium salts and process for making them |
US5015373A (en) * | 1988-02-03 | 1991-05-14 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
US5141634A (en) * | 1988-02-03 | 1992-08-25 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
US5205929A (en) * | 1988-02-03 | 1993-04-27 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3488922A (en) * | 1968-10-10 | 1970-01-13 | Du Pont | Method and apparatus for chromatographic separations with superficially porous glass beads having sorptively active crusts |
US3722181A (en) * | 1970-05-22 | 1973-03-27 | Du Pont | Chromatographic packing with chemically bonded organic stationary phases |
US4054432A (en) * | 1976-06-11 | 1977-10-18 | Wright State University | Polymer lined capillary column and method for producing same |
-
1979
- 1979-02-22 US US06/014,131 patent/US4209554A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3488922A (en) * | 1968-10-10 | 1970-01-13 | Du Pont | Method and apparatus for chromatographic separations with superficially porous glass beads having sorptively active crusts |
US3722181A (en) * | 1970-05-22 | 1973-03-27 | Du Pont | Chromatographic packing with chemically bonded organic stationary phases |
US4054432A (en) * | 1976-06-11 | 1977-10-18 | Wright State University | Polymer lined capillary column and method for producing same |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4473505A (en) * | 1980-02-12 | 1984-09-25 | Exxon Research And Engineering Co. | Phosphine and phosphonium compounds and catalysts |
US4620020A (en) * | 1984-04-21 | 1986-10-28 | Hoecht Aktiengesellschaft | Bis-phosphonium salts and process for making them |
US5015373A (en) * | 1988-02-03 | 1991-05-14 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
US5141634A (en) * | 1988-02-03 | 1992-08-25 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
US5205929A (en) * | 1988-02-03 | 1993-04-27 | Regents Of The University Of Minnesota | High stability porous zirconium oxide spherules |
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